Activation of Ammonia by a Carbene-Stabilized Dithiolene Zwitterion
Yuzhong Wang, Phuong M. Tran, Mitchell E. Lahm, Yaoming Xie, Pingrong Wei, Earle R. Adams, John Glushka, Zichun Ren, Vladimir V. Popik, Henry F. Schaefer, Gregory H. Robinson
Abstract
A carbene-stabilized dithiolene zwitterion (3) activates ammonia, affording 4• and 5, through both single-electron transfer (SET) and hydrogen atom transfer (HAT). Reaction products were characterized spectroscopically and by single-crystal X-ray diffraction. The mechanism of the formation of 4• and 5 was probed by experimental and computational methods. This discovery is the first example of metal-free ammonia activation via HAT.
Topics & Concepts
ZwitterionChemistryCarbeneAmmoniaHydrogen atomSingle crystalPhotochemistryElectron transferCrystallographyMoleculeCatalysisOrganic chemistryGroup (periodic table)N-Heterocyclic Carbenes in Organic and Inorganic ChemistryFluorine in Organic ChemistrySynthesis and characterization of novel inorganic/organometallic compounds